Water-insoluble azo-dyestuff and fiber dyed therewith



Patented July 4, 1933 UNHTED STATES PAT HER-MANN WAGNER, OF SODEN-ON-THE-TAUNUS, AND HERBERT KTLUAGKER, F FRANK- FORT-ON-THE-MAIN, GERMANY, ASSIGNORS TO GENERAL ANILINE VJORKS, INCL, OF NEW YORK, N. Y., A CORPORATION OF DELAWARE WATER-INSOLUBLE .AZO-DYESTUFF AND FIBER. DYEID 'II-IEBJEWITI-I Ho Drawing. Application filed March 12, 1931, Serial No. 522,172, and in NH2 1 6 ,-CH3

H 5 3 on;

wherein X stands for halogen.

A great number of the combinations thus obtainable have a fastness to kier-boiling (boiling for 4 hours under a pressure of 1 atmospheres with 160 cc. of caustic soda solution of Be. in 40,000 cc., of water per 1000 grams of material to be kier-boiled) which, hitherto, has been very rare with dyestufis of the ice color group. Others of the combina- 9 tions fulfill high requirements in respect of fastness to light and several of them combine an enhanced fastness to kier boiling with good fastness to light. Besides all of them have good properties of fastness to boiling lye (boiling for 6 hours at atmospheric pressure with 100 cc. of caustic soda solution of &0 Be. in 10,000 cc. of water per 1000 grams of material) and to chlorine. Furthermore, a great many of the dyestuffs obtainable according to the present invention have a vivid and clear Turkey red tint very much in demand by the cotton dyers. By the present invention it is possible to obtain dyeings of a Turkey red tint which is at the same time fast to kier boil- 5 ing and to light; they supply a long felt want in the ice-color dyeing industry.

The new dyestuffs can be made in the usual manner by dyeing or printing them on the fiber or by producing them in substance or on 0 any of the usual substrata adapted for the Germany March 20, 1930.

production of lakes.

The dyestuffs obtained by this invention correspond wlth the following general formula CH3 CH3 wherein X represents halogen and R represents a residue of the benzene or naphthalene series, the hydrogen atoms of which may be substituted but must not contain any free sulfonicor carboxylic acid groups.

The following examples serve to illustrate the invention, but they are not intended to limit it thereto:

Dyeing prescriptions for Examples 1 and Z grams of well boiled cotton yarn are treated for half an hour in the grounding liquor, the yarn is wound, well hydro-e1; tracted or squeezed and dyed for half an hour in the dye-bath. The dyed cotton yarn is then rinsed several times, soaped at boiling temperature and rinsed again.

EXAMPLE 1 (a) Grounding liquor 5 grams of 2 3-hydroxynaphthoyl-1- amino-2-methoxyi-chlorobenzene are made into a paste with 10 cc. of Turkey red oil (50 per cent. strength) and 10 cc. of caustic soda solution of 3 L Be. and the whole is dissolved by pouring 1 liter of boiling water over it.

After the solution hascooled to 50 C. 5 cc. of

formaldehyde of 30 per cent. strength are added.

(6) Dye-bath 2 grams of crystallized sodium acetate and the whole is made up to 1 liter.

A vivid bluish Turkey red of good fastness to chlorine and light is obtained. By boiling the dyed materialfor 4 hours under a pressure of 1 atmospheres in a solution containing 4 grams of NaOH per liter, it also shows a good fastness to kier boiling.

The dyestuif corresponds withthe following formula CH; CH:

O H EH:

OCH;

o 0.1m o1 EXALIPLE 2 (a) Grounding liquor The groundingliquor is prepared as in' Example 1 by using, however, 5 grams of 2 3 -hydroxynaphthoy1 1 -amino -4-chloro- 2 5'-dimethoxy benzene.

(b) Dye-bath The dyebath is the same as in Example 1. There is obtained a vivid clear Turkey red of good fastness to chlorine and Weather which at the same time fulfils the high requirements in respect to fastness to light. By boiling the dyed material for 4 hours under a pressure of 1 atmospheres in a solution containing 4 grams of NaOH per liter, it also shows a good fastness to kier boiling.

The dyestuif corresponds with the following formula on; om

cons-Q01 0on5 EXAMPLE 3 rendered neutral to Congo paper by meansof about 20 grams of crystallized sodium acetate.

This solution is run into the arylide suspension prepared as above described. After stirring for a prolonged time the formation of the dyestufi is finished. It is filtered by suction and well washed with water.

The dyestuff forms a bluish-red paste of goodfastness to light and corresponds with the following formula CH3 CH3 OCH:

coma-O mentioned therein:

Diazotizing component Coupling component Tint (1) 1-amino-4-chloro-2z3r5- 2:3-hydroxynaphthoyl-l- Clear, very ttimethylbenzene amino 2 methylbenbluish red zene (2) l-amino 4-ehloro-2z3z5- 2:3-hydroxynaphthoyl-1- Vivid midtrimethylbenzene amino 2 methoxyred benzene (3) l-amino-4-ehloro-2:3:5- 2:3-hydroxynaphthoyl-1- Very bluish trimethylbenzene amino 2 methyl 4- red chlorobenzene (4) 1-amino-4-ch1oro-2z3z5- 2:3-hydroxynaphthoyl-1- Vivid bluish trimethylbenzene amino 2-methoxy-5- '1 u r k e y chlorobenzene red (5) 1-amino-4-chloro-2z3z5- 2:3-hydroxynaphthoyl-Y- Ruby red trimethylbenzene amino 2:3-dimethoxybenzene (6) 1-amino-4-ch1oro-2:3:5- 2:3-hydroxynaphthoyl-1- Vivid Turtrimethylbenzene amino-4-ci1loro-2-3:5- key red trimethylbenzene (7) lamino-4-chloro-2z3:5- 2z3hydroxynaphthoyl l- Vivid 'Iu rtrimethylbenzene amino 4 ehloro 2:5- key red diethoxybenzene (8) 1-amino-4-chloro-2z3z5- 2:H-hydroxynaphthoyLU- Vivid bluish trimethylbenzene amino-4-chloro-3.-me- T u r k c y thyl6'-methoxybenzene rod (9) l-am1no4-chloro-2:3:5 2:3-hydr0xynaphthoyl-l- Ruby red trimethylbenzene aminonaphthalene (10) l amino 4 chloro- 2z3-hydroxynaphthoyl-2- Ruby red 2z3z5- trimethylbenzene aminonaphthalcne (l1) 1 amino 4 chloro- 2:3-hydroxynaphthoyl-l Vivid Bor- 2:3:5-trimethy1benzene a]n1i1no-l-metlioxynaplidenux red t 1:: one (l2) 1 amino 4 chloro- 2:3-hydroxynephthoyl-2'- Vivid Tur- 2z3z5-tnmethy1benzene a111ni1no-3-methorynaphkey red t a one (l3) 1 amino 4 -brom0- 2:3-hydroxynaphthoyl-l- Vivid bluish 2:3:5-trimethylhenzene aminozzy-dimethorgy- 'I u r k e y 4-chlorobenzene red (14) l amino -4 bromo- 2:3-l1ydroxynaphtl1oyl-2- Vivid 'lur- 2:3:5-trimethylbenzene almilno-y-methoxynaphkey red t a one 7 (l5) 1-amino-4-iodo'2:3:5- 2:B-h dmXynaphthOyI-Y- Vivid bluish trunethylbenzene amino 2 ethoxyben- T u l k e y v zone red (l6) 1-amino-4-1odo-2:3:5- 2:3-hydroXynaphthoyl-Y- Bluish red tnmethylbenzene amino-2-5-dimethoxybenzene The bases mentioned in the above examples which have hitherto not been described in the pertaining art have the following properties:

1-aminolchloro-2 3 5-trimethylbenzene is obtainable by chlorination of l-ami- 110-2 3 5-trimethylbenzene. It crystallizes from petroleum ether in long, white loose needles melting at 11011l C. Itis scarcely volatile with steam, easily soluble in organic solvents.

1 -amino-4t-bromo-2 3 S-trimethylbenzene is obtainable by bromination of Lamino-2: 3: 5-trimethylbenzene. It crystallizes from petroleum ether in long, white, brilliant needles melting at 116-117 C. It is easily soluble in organic solvents, very sparingly volatile with steam.

1-aminol-iodo-2 3: fi-trimethylbenzene is obtainable by iodinating 1-amino-2 3 -trimethylbenzene. It crystallizes from alcohol in white needles, melting at 132133 C. It is easlly soluble in organic solvents, very I sparingly volatile with steam.

Certain of the parent materials referred to in the foregoing examples and table, which are not generally known, may be made as follows:

2 3-hydroxynaphthoyl-1-amino-4-chloro- 2: 5-dimethoxy-benzene can be prepared according to the statements in the U. S. A. application, Ser. No. 343,841, filed on March 1, 1929 in the name of Leopold Laska and Arthur Zitscher.

.acid

5 tainable as described on page 146 of Liebigs Annalen der Chemie, Vol. 215) and then chlorinating the reduction product in paraposition.

2 3-hydroxynaphthoyl-1-amino-4l-chloro- 3-methyl-6-methoxybenzene may be obtained by condensing with 2 3-hydroxynaphthoic acid the base prepared according to the statements given on page 396 of Recueil des Travaux chimiques des Pays-Bas, Vol.

2: 3-hydroxynaphthoyl-1-an1ino-4; methoXy-naphthalene is obtainable according to the statements in the U. S. A. application Ser. No. 340,023 filed on February 14:, 1929 in the name of Wilhelm Fitzky.

We claim:

1. As new products, the water-insoluble azo-dyestufis of the following general formula:

CH3 CH3 n QX OH Ha CO.NH.R

wherein Xrepresents halogen and R represents a residue of the benzene or naphthalene series, which must not contain any free sulfonioor carboxylic acid groups, dyeing vivid red shades and being distinguished by their good fastness properties, particularly by their good fastness to kier-boiling, to chlorine and to light.

2. As new products, the Water-insoluble aZo-dyestuffs of the following general formula:

CH3 CH3 CH3 on oo. NH. R

wherein R represents a residue of the benzene series, which must not contain any free sulfonicor carboxyhc acid groups, dyemg vivid red shades and being distinguished by their good fastness properties, particularly by their good fastness to kier-boiling, to chlorine and to light.

4. As a new product, the water-insoluble azo-dyestuff of the following formula boiling to chlorine and to light.

being distinguished by its good fast-ness proptures. erties, particularly by its good fastness to 5. As a new product, the water-insoluble aZo-dyestufi of the following formula:

dyeing a vivid bluish Turkey red shade and kier-boiling, to chlorine andto light.

6. As anew product, the water-insoluble on, on,

dyeing a bluish red shade and being distinguished by its good fastness properties, particularly by its good fastness to kier-boiling, to chlorine and to light.

7. Fiber dyed with the azo-dyestufis as claimed in claim l.

8. Fiber dyed with the azo-dyestuffs as claimed in claim 2.

9. Fiber dyed with the azo-dyestufl's as claimed in claim 3.

10. Fiber dyed with the azo-dyestufi as claimed in claim 4.

11. Fiber dyed with the azo-dyestuif as claimed in claim 5.

12. Fiber dyed with the azo-dyestuff as claimed in claim 6. y

In testimony whereof, we afiix our signa- HERMANN XVAGNER. I HERBERT KRAGKER. 

